CN111574686A - Star-shaped multi-response shape memory polyurethane composite material and preparation method thereof - Google Patents
Star-shaped multi-response shape memory polyurethane composite material and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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Abstract
The invention provides a star-shaped multiple-response shape memory polyurethane composite material, which has a structural formula as follows:
wherein n, k and m all represent the polymerization degree and can be any positive integer;
is composed of
R is
The multiple response shape memory polyurethane composite material prepared by the invention utilizes the photo-induced isomeric azobenzene as a light-operated switch, and can realize the light-heat double response in the real sense.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a star-shaped multi-response shape memory polyurethane composite material and a preparation method thereof.
Background
The shape memory material refers to a kind of intelligent material which changes its initial shape under a certain condition, fixes a temporary shape, and then returns to a certain initial shape under a certain condition stimulation, and has a lot of advantages of shape fixation, recovery performance, large deformation amount of the material and the like, thereby gaining wide attention.
At present, shape memory materials which respond under a stimulus are mainly researched, but the materials can hardly meet the use requirements in the field of intelligent materials. Therefore, the development of shape memory materials with multiple responses has become an urgent need, and is a hot spot. The multiple-response shape memory materials developed and designed at present are mostly realized by light-heat and electricity-heat, and the multiple-response performance realized by heat generated by light or electricity is essentially limited by single heat.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a star-shaped multi-response shape memory polyurethane composite material and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: a star-shaped multi-response shape memory polyurethane composite material is characterized in that the structural formula of the composite material is as follows:
wherein n, k and m all represent the polymerization degree and can be any positive integer;
is composed of
R is
The preparation method of the star-shaped multi-response shape memory polyurethane composite material comprises the following steps:
(1) weighing 2.5-3.5g of SMPU10, placing in a glass bottle, adding DMF solvent, placing the glass bottle in an oil bath kettle at 80 ℃, and stirring;
(2) after the SMPU10 is completely dissolved, 1.0-2.5g of Azo11 is added into the mixture for reaction for 2 hours;
(3) and after the reaction is finished, pouring the reaction solution into a preheated mold, and placing the mold in an oven at 80 ℃ for drying for 8-10h to obtain the multi-response shape memory polyurethane composite material.
Further, the synthetic method of the SMPU10 is as follows;
(1) prepolymerization reaction: weighing 5.00g of PCL, placing the PCL in a reactor, adding 18-25mL of LDMF and 3-6 drops of hexamethylene diisocyanate, adding a catalyst, placing the reactor in an oil bath pot, stirring and heating to 80-90 ℃, wherein the stirring speed is 400-500 r/min, adding 0.8-0.9mL of hexamethylene diisocyanate into the reactor, and reacting for 1 hour;
(2) chain extension reaction: at the reaction temperature, adding 2.6-3.0g of solid N, N dihydroxyethyl isonicotine into the reactor, adding 2.0-5.0mL of hexamethylene diisocyanate, and reacting for 2-4 h;
(3) and (3) crosslinking reaction: adding 0.3-0.5g of glycerol into the reaction liquid in the step (2), and reacting for 2 hours;
(4) film forming: and pouring the liquid after the reaction into a preheated mould, uniformly distributing the liquid on the mould, and placing the mould in an oven at 80 ℃ for drying for 8-20h to obtain the shape memory polyurethane SMPU 10.
Furthermore, the molecular weight of the PCL is 2000, and the PCL needs to be placed in an oven at 80 ℃ for drying treatment before use.
Further, the catalyst is dibutyltin dilaurate.
Further, the synthetic method of Azo11 comprises the following steps:
(1) putting 5.0g of Azoba, 50mL of absolute ethyl alcohol and 2.0g of potassium carbonate into a reactor, adding 4.3-4.5g of bromoundecane into the reactor while stirring, and putting the reactor into a 65 ℃ oil bath to react for 12 hours;
(2) after the reaction is finished, the reaction solution is poured into 1000mL of ice water while the reaction solution is hot, stirred, filtered, washed and dried to obtain solid Azo 11.
Further, the synthetic method of the Azoba comprises the following steps:
(1) preparing a sodium hydroxide solution and a glucose solution;
(2) weighing 10.0-15.0g of p-nitrobenzoic acid monomer into a reactor, adding the sodium hydroxide solution into the reactor for dissolution, placing the reactor into an oil bath kettle at 50-60 ℃, heating for 10-20min, adding the glucose solution into the reactor, and reacting at 50-60 ℃ for 8-10 h;
(3) and after the reaction is finished, pouring out the reaction liquid, cooling to room temperature, adding a dilute acetic acid solution with the mass fraction of 15% into the reaction liquid, adjusting the pH value to 6, performing suction filtration and washing, then adding the solution into a hot potassium carbonate solution, performing suction filtration again after the potassium carbonate solution is cooled and a solid is separated out, washing the obtained solid to be neutral by water, and drying to obtain a light yellow powdery solid, namely the Azoba.
Compared with the prior art, the invention has the following beneficial effects:
in the experiment, Polycaprolactone (PCL), N-methyldiethanolamine (BINA), Glycerol (GI) and Hexamethylene Diisocyanate (HDI) are used as main raw materials, shape memory polyurethane (SMPU10) with thermal response is prepared by a solution polymerization method, and then SMPU10 is blended with a compound with an undecyloxy azobenzene carboxylic acid (Azo11) and a photoisomerization group, so that the shape memory polyurethane composite material with multiple responses is prepared. The structure and properties thereof were investigated by 1H NMR, FT-IR, XRD, TG, DSC and the like. The results show that: the experiment successfully synthesizes the multi-response shape memory polyurethane composite material, has light response and thermal response at the same time, provides a new research basis for the application and development of the multi-response shape memory material, and expands the field of the multi-response shape memory material.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a sample of SMPU 10;
FIG. 2 is an infrared spectrum of the star-shaped multi-response shape memory polyurethane composite material of the present invention;
FIG. 3 is an XRD pattern of the star-shaped multi-response shape memory polyurethane composite material of the present invention;
FIG. 4 is a thermogravimetric plot of a star multi-response shape memory polyurethane composite of the present invention, wherein (a) the TG plot and (b) the DTG plot;
FIG. 5 is a DSC graph of a star-shaped multi-response shape memory polyurethane composite of the present invention, wherein (a) the first temperature decreasing graph and (b) the second temperature increasing graph are shown;
FIG. 6 is a process of thermal response shape memory recovery of SMPU 10;
FIG. 7 is a thermally responsive shape memory recovery process of A-SMPU 10;
FIG. 8 shows the sample pretreatment process of A-SMPU 10;
FIG. 9 is a graph of the deformation of A-SMPU10 under UV illumination;
FIG. 10 illustrates the thermally responsive shape memory recovery process of A-SMPU 10.
Detailed Description
The process of the present invention will be described in detail with reference to specific examples. The star-shaped multi-response shape memory polyurethane composite material can be abbreviated as PSMPun, and the final product of the invention is subjected to a series of characterization such as infrared, TG and DSC. In the present invention, SMPU10 represents a shape memory polyurethane having a hard segment content of 10%, the Chinese name of Azo11 is undecyloxyazobenzene paracarboxylic acid, the Chinese name of Azoba is azobenzene-4, 4' -dicarboxylic acid, the Chinese name of hexamethylene diisocyanate is HDI, the Chinese name of dibutyltin dilaurate is DBTL, the Chinese name of DMF is N, N-dimethylformamide, and the Chinese name of N, N-hydroxyethylisonicotinine is BINA.
Firstly, preparation of star-shaped multi-response shape memory polyurethane composite material
Example 1
1.1) Synthesis of SMPU10
(1) Weighing 5.00g of molten PCL-2000(2000 represents molecular weight) by using an electronic analytical balance, placing the molten PCL-2000 in a three-neck flask, adding 18mL of N, N Dimethylformamide (DMF) serving as a solvent into the flask, 3-5 drops of Hexamethylene Diisocyanate (HDI), then adding 2-3 drops of dibutyltin Dilaurate (DBTL) serving as a catalyst, and plugging bottle mouths on two sides by using a flanging plug to prevent DMF volatilization and air from entering; mounting the three-neck flask on an iron support, installing an electric stirrer and an oil bath pot (the height of the silicone oil should be higher than that of the flask body 2/3), opening the electric stirrer to uniformly mix the raw materials, opening the oil bath pot to 80 ℃, and continuing stirring in the heating process (the rotating speed of the electric stirrer is 400 r/min); when the temperature of the oil bath is increased to 80 ℃, 0.8mL of HDI is sucked by a 2mL needle syringe and slowly added into the three-neck flask; reacting for 1h, and carrying out prepolymerization;
(2) keeping the temperature at 80 ℃, adding 2.60g of N, N-hydroxyethyl isonicotine (BINA) as a chain extender into a three-neck flask, slowly adding 2.0mL of HDI, and fully reacting for two hours to carry out chain extension;
(3) adding 0.3g of Glycerol (GI) to react for two hours, and carrying out crosslinking;
(4) placing a mould in a drying oven in advance for preheating, taking out a three-neck flask from an iron support after two-hour cross-linking reaction, pouring an SMPU10 solution prepared in the flask into the preheated mould from a side bottleneck, shaking the mould to enable the solution to be distributed uniformly, slightly dropping a plurality of lower moulds on a table top to eliminate small bubbles in the solution, then placing the mould into the drying oven at 80 ℃ for drying for 8 hours to fully evaporate DMF solvent, and demoulding to obtain SMPU 10.
1.2) preparation of undecyloxyazobenzene p-Carboxylic acid (Azo11)
Weighing 50.0g of NaOH and 240mL of deionized water, and putting the NaOH and the deionized water into a beaker to prepare a sodium hydroxide solution; then 100.0g of glucose and 150mL of deionized water are weighed and placed in a beaker to prepare a glucose solution; dissolving 13g of p-nitrobenzoic acid monomer by using the prepared sodium hydroxide solution, adding the p-nitrobenzoic acid monomer into a three-neck flask, installing the three-neck flask on an iron stand, opening an electric stirrer, and heating for 10-20min by using an oil bath kettle at 50 ℃; slowly dripping the glucose solution into a three-neck flask after 10min (the dripping process needs to be completed within 30 min), setting the reaction temperature to be 50-60 ℃, and reacting for 8.5 h; after 8.5 hours, pouring out the sample, cooling to room temperature, adding 15% dilute acetic acid solution to adjust the pH to about 6, carrying out suction filtration to obtain solid, washing with water for multiple times, then adding into hot potassium carbonate solution, cooling the hot potassium carbonate solution to separate out the solid, and carrying out secondary suction filtration; the solid obtained by suction filtration was washed repeatedly with water until neutral and then placed in a drying oven set at 100 ℃ for 24h to dry the product, yielding 8.4g of a pale yellow powder with a yield of about 80%. The product was prepared at this point as azobenzene-4, 4' -dicarboxylic acid (Azoba).
Weighing 5.0g of the Azoba synthesized in the previous step, 50mL of absolute ethyl alcohol and 2.0g of potassium carbonate, putting the obtained mixture into a 250mL three-neck flask, plugging the bottle mouths on two sides with a turning plug, opening an electric stirrer, and adding 4.3g of bromoundecane under stirring;
placing the three-neck flask in an oil bath kettle, setting the temperature to 65 ℃ and refluxing the reactants for 12 hours; after 12h, the hot reaction solution was poured into 1000mL of ice water and stirred, which was followed by removal of the potassium carbonate; filtering, washing the obtained solid with a large amount of petroleum ether, and removing unreacted bromoundecane; performing secondary suction filtration, and drying the obtained solid in a drying oven; to obtain a product of higher purity, purification is carried out by column chromatography, first using petroleum ether: dichloromethane ═ 2: 1 (volume ratio) as a solvent, the first component in the sample was removed, and then petroleum ether: dichloromethane elution ═ 1: 2 (volume ratio), collecting the second component; the collected second fractions were dried to yield 8.7g of a light yellow solid in about 94% yield, which gave the product as Azo 11.
1.3) preparation of multiple-response shape memory polyurethane composite A-SMPU10
(1) Weighing 2.5g of SMPU10, placing the SMPU10 in a glass bottle, adding a DMF solvent into the glass bottle, placing the glass bottle in an oil bath kettle at the temperature of 80 ℃, and stirring;
(2) after the SMPU10 is completely dissolved, 1.012g of Azo11 is added into the mixture to react for 2 hours;
(3) after the reaction is finished, pouring the reaction solution into a preheated mold, and placing the mold in an oven at 80 ℃ for drying for 8 hours to obtain the multiple response shape memory polyurethane composite material named A-SMPU 10.
Example 2
1.1) Synthesis of SMPU10
(1) Weighing 5.00g of molten PCL-2000(2000 represents molecular weight) by using an electronic analytical balance, placing the molten PCL-2000 in a three-neck flask, adding 19mL of N, N Dimethylformamide (DMF) serving as a solvent into the flask, 3-5 drops of Hexamethylene Diisocyanate (HDI), then adding 2-3 drops of dibutyltin Dilaurate (DBTL) serving as a catalyst, and plugging bottle mouths on two sides by using a flanging plug to prevent DMF volatilization and air from entering; mounting a three-neck flask on an iron support, installing an electric stirrer and an oil bath pot (the height of silicone oil should be higher than that of a flask body 2/3), opening the electric stirrer to uniformly mix the raw materials, opening the oil bath pot to 90 ℃, and continuing stirring in the heating process (the rotating speed of the electric stirrer is 450 r/min); when the temperature of the oil bath is increased to 90 ℃, 0.9mL of HDI is sucked by a 2mL needle syringe and slowly added into the three-neck flask; reacting for 1h, and carrying out prepolymerization;
(2) keeping the temperature at 80 ℃, adding 2.70g of N, N-hydroxyethyl isonicotine (BINA) as a chain extender into a three-neck flask, slowly adding 3.0mL of HDI, and fully reacting for 2h to carry out chain extension;
(3) adding 0.40g of Glycerol (GI) to react for two hours, and carrying out crosslinking;
(4) placing a mould in a drying oven in advance for preheating, taking out a three-neck flask from an iron support after two-hour cross-linking reaction, pouring an SMPU10 solution prepared in the flask into the preheated mould from a side bottleneck, shaking the mould to enable the solution to be distributed uniformly, slightly throwing a plurality of lower moulds on a table top to eliminate small bubbles in the solution, then placing the mould into the drying oven at 80 ℃ for drying for 12 hours to fully evaporate DMF solvent, and demoulding to obtain the SMPU 10.
1.2) preparation of undecyloxyazobenzene p-Carboxylic acid (Azo11)
Weighing 50.0g of NaOH and 240mL of deionized water, and putting the NaOH and the deionized water into a beaker to prepare a sodium hydroxide solution; then 100.0g of glucose and 150mL of deionized water are weighed and placed in a beaker to prepare a glucose solution; dissolving 13g of p-nitrobenzoic acid monomer by using the prepared sodium hydroxide solution, adding the p-nitrobenzoic acid monomer into a three-neck flask, installing the three-neck flask on an iron stand, opening an electric stirrer, and heating for 10-20min by using an oil bath kettle at 50 ℃; slowly dripping the glucose solution into a three-neck flask after 10min (the dripping process needs to be completed within 30 min), setting the reaction temperature to be 50-60 ℃, and reacting for 8.0-10.0 h; after 8.5 hours, pouring out the sample, cooling to room temperature, adding 15% dilute acetic acid solution to adjust the pH to about 6, carrying out suction filtration to obtain solid, washing with water for multiple times, then adding into hot potassium carbonate solution, cooling the hot potassium carbonate solution to separate out the solid, and carrying out secondary suction filtration; the solid obtained by suction filtration was washed repeatedly with water until neutral and then placed in a drying oven set at 100 ℃ for 24h to dry the product, yielding 8.4g of a pale yellow powder with a yield of about 80%. The product was prepared at this point as azobenzene-4, 4' -dicarboxylic acid (Azoba).
Weighing 5.0g of the Azoba synthesized in the previous step, 50mL of absolute ethyl alcohol and 2.0g of potassium carbonate, putting the obtained mixture into a 250mL three-neck flask, plugging the bottle mouths on two sides with turning plugs, opening an electric stirrer, and adding 4.4g of bromoundecane under stirring;
placing the three-neck flask in an oil bath kettle, setting the temperature to 65 ℃ and refluxing the reactants for 12 hours; after 12h, the hot reaction solution was poured into 1000mL of ice water and stirred, which was followed by removal of the potassium carbonate; filtering, washing the obtained solid with a large amount of petroleum ether, and removing unreacted bromoundecane; performing secondary suction filtration, and drying the obtained solid in a drying oven; to obtain a product of higher purity, purification is carried out by column chromatography, first using petroleum ether: dichloromethane ═ 2: 1 (volume ratio) as a solvent, the first component in the sample was removed, and then petroleum ether: dichloromethane elution ═ 1: 2 (volume ratio), collecting the second component; the collected second fractions were dried to yield 8.7g of a light yellow solid in about 94% yield, which gave the product as Azo 11.
1.3) preparation of multiple-response shape memory polyurethane composite material B-SMPU10
(1) Weighing 3.0g of SMPU10, placing in a glass bottle, adding DMF solvent, placing the glass bottle in an oil bath kettle at 80 ℃, and stirring;
(2) after the SMPU10 is completely dissolved, 1.520g of Azo11 is added into the mixture to react for 2 hours;
(3) after the reaction is finished, pouring the reaction solution into a preheated mold, and placing the mold in an oven at 80 ℃ for drying for 8 hours to obtain the multi-response shape memory polyurethane composite material named as B-SMPU 10.
Example 3
1.1) Synthesis of SMPU10
(1) 5.00g of PCL-2000(2000 represents molecular weight) in a molten state is weighed by an electronic analytical balance and placed in a three-neck flask, 20mL of N, N Dimethylformamide (DMF) is added into the flask as a solvent, 5-6 drops of Hexamethylene Diisocyanate (HDI) are added, 2-3 drops of dibutyltin Dilaurate (DBTL) are added as a catalyst, and bottle mouths on two sides are plugged by a flanging plug to prevent DMF volatilization and air entering; mounting a three-neck flask on an iron support, installing an electric stirrer and an oil bath pot (the height of silicone oil should be higher than that of a flask body 2/3), opening the electric stirrer to uniformly mix the raw materials, opening the oil bath pot to 85 ℃, and continuing stirring in the heating process (the rotating speed of the electric stirrer is 500 r/min); when the temperature of the oil bath is increased to 80 ℃, 0.90mL of HDI is sucked by a 2mL needle syringe and slowly added into the three-neck flask; reacting for one hour, and performing prepolymerization;
(2) keeping the temperature at 80 ℃, adding 2.8g of N, N-hydroxyethyl isonicotine (BINA) as a chain extender into a three-neck flask, slowly adding 4.0mL of HDI, and fully reacting for two hours to carry out chain extension;
(3) adding 0.45g of Glycerol (GI) to react for two hours, and carrying out crosslinking;
(4) placing a mould in a drying oven in advance for preheating, taking out a three-neck flask from an iron support after two-hour cross-linking reaction, pouring an SMPU10 solution prepared in the flask into the preheated mould from a side bottleneck, shaking the mould to enable the solution to be distributed uniformly, slightly dropping a plurality of lower moulds on a table top to eliminate small bubbles in the solution, then placing the mould into the drying oven at 80 ℃ for drying for 8 hours to fully evaporate DMF solvent, and demoulding to obtain SMPU 10.
1.2) preparation of undecyloxyazobenzene p-Carboxylic acid (Azo11)
Weighing 50.0g of NaOH and 240mL of deionized water, and putting the NaOH and the deionized water into a beaker to prepare a sodium hydroxide solution; then 100.0g of glucose and 150mL of deionized water are weighed and placed in a beaker to prepare a glucose solution; dissolving 13g of p-nitrobenzoic acid monomer by using the prepared sodium hydroxide solution, adding the p-nitrobenzoic acid monomer into a three-neck flask, installing the three-neck flask on an iron stand, opening an electric stirrer, and heating for 10min by using an oil bath kettle at 50 ℃; slowly dripping the glucose solution into a three-neck flask after 10min (the dripping process needs to be completed within 30 min), setting the reaction temperature to be 50-60 ℃, and reacting for 8.5 h; after 8.5 hours, pouring out the sample, cooling to room temperature, adding 15% dilute acetic acid solution to adjust the pH to about 6, carrying out suction filtration to obtain solid, washing with water for multiple times, then adding into hot potassium carbonate solution, cooling the hot potassium carbonate solution to separate out the solid, and carrying out secondary suction filtration; the solid obtained by suction filtration was repeatedly washed with water to neutrality and then dried in a drying oven set at 100 ℃ for 24 hours, yielding 8.4g of a pale yellow powdery product with a yield of about 80%. The product was prepared at this point as azobenzene-4, 4' -dicarboxylic acid (Azoba).
Weighing 5.0g of the Azoba synthesized in the previous step, 50mL of absolute ethyl alcohol and 2.0g of potassium carbonate, putting the obtained mixture into a 250mL three-neck flask, plugging the bottle mouths on two sides with turning plugs, opening an electric stirrer, and adding 4.5g of bromoundecane under stirring;
placing the three-neck flask in an oil bath kettle, setting the temperature to 65 ℃ and refluxing the reactants for 12 hours; after 12h, the hot reaction solution was poured into 1000mL of ice water and stirred, which was followed by removal of the potassium carbonate; filtering, washing the obtained solid with a large amount of petroleum ether, and removing unreacted bromoundecane; performing secondary suction filtration, and drying the obtained solid in a drying oven; to obtain a product of higher purity, purification is carried out by column chromatography, first using petroleum ether: dichloromethane ═ 2: 1 (volume ratio) as a solvent, the first component in the sample was removed, and then petroleum ether: dichloromethane elution ═ 1: 2 (volume ratio), collecting the second component; the collected second fractions were dried to yield 8.7g of a light yellow solid in about 94% yield, which gave the product as Azo 11.
1.3) preparation of multiple-response shape memory polyurethane composite A-SMPU10
(1) Weighing 3.5g of SMPU10, placing in a glass bottle, adding DMF solvent, placing the glass bottle in an oil bath kettle at 80 ℃, and stirring;
(2) after the SMPU10 is completely dissolved, 2.5g of Azo11 is added into the mixture for reaction for 2 hours;
(3) after the reaction is finished, pouring the reaction solution into a preheated mold, and placing the mold in an oven at 80 ℃ for drying for 10 hours to obtain the multi-response shape memory polyurethane composite material named A-SMPU 10.
Example 4
1.1) Synthesis of SMPU10
(1) 5.00g of PCL-2000(2000 represents molecular weight) in a molten state is weighed by an electronic analytical balance and placed in a three-neck flask, 25mL of N, N Dimethylformamide (DMF) is added into the flask as a solvent, 5-6 drops of Hexamethylene Diisocyanate (HDI) are added, 2-3 drops of dibutyltin Dilaurate (DBTL) are added as a catalyst, and bottle mouths on two sides are plugged by turning plugs to prevent DMF volatilization and air from entering; mounting the three-neck flask on an iron support, installing an electric stirrer and an oil bath pot (the height of silicone oil should be higher than that of a flask body 2/3), opening the electric stirrer to uniformly mix the raw materials, opening the oil bath pot to 80 ℃, and continuing stirring in the heating process (the rotating speed of the electric stirrer is not lower than 400 r/min); when the temperature of the oil bath is increased to 80 ℃, 0.85mL of HDI is sucked by a 2mL needle syringe and slowly added into the three-neck flask; reacting for 1h, and carrying out prepolymerization;
(2) keeping the temperature at 80 ℃, adding 3.0g of N, N-hydroxyethyl isonicotine (BINA) serving as a chain extender into a three-neck flask, slowly adding 5.0mL of HDI, and fully reacting for two hours to carry out chain extension;
(3) adding 0.5g of Glycerol (GI) to react for two hours, and carrying out crosslinking;
(4) placing a mould in a drying oven in advance for preheating, taking out a three-neck flask from an iron support after two-hour cross-linking reaction, pouring an SMPU10 solution prepared in the flask into the preheated mould from a side bottleneck, shaking the mould to enable the solution to be distributed uniformly, slightly dropping a plurality of lower moulds on a table top to eliminate small bubbles in the solution, then placing the mould into the drying oven at 80 ℃ for drying for 8 hours to fully evaporate DMF solvent, and demoulding to obtain SMPU 10.
1.2) preparation of undecyloxyazobenzene p-Carboxylic acid (Azo11)
Weighing 50.0g of NaOH and 240mL of deionized water, and putting the NaOH and the deionized water into a beaker to prepare a sodium hydroxide solution; then 100.0g of glucose and 150mL of deionized water are weighed and placed in a beaker to prepare a glucose solution; dissolving 13g of p-nitrobenzoic acid monomer by using the prepared sodium hydroxide solution, adding the p-nitrobenzoic acid monomer into a three-neck flask, installing the three-neck flask on an iron stand, opening an electric stirrer, and heating for 10min by using an oil bath kettle at 50 ℃; slowly dripping the glucose solution into a three-neck flask after 10min (the dripping process needs to be completed within 30 min), setting the reaction temperature to be 50-60 ℃, and reacting for 8.5 h; after 8.5 hours, pouring out the sample, cooling to room temperature, adding 15% dilute acetic acid solution to adjust the pH to about 6, carrying out suction filtration to obtain solid, washing with water for multiple times, then adding into hot potassium carbonate solution, cooling the hot potassium carbonate solution to separate out the solid, and carrying out secondary suction filtration; the solid obtained by suction filtration was repeatedly washed with water to neutrality and then dried in a drying oven set at 100 ℃ for 24 hours, yielding 8.4g of a pale yellow powdery product with a yield of about 80%. The product was prepared at this point as azobenzene-4, 4' -dicarboxylic acid (Azoba).
Weighing 5.0g of the Azoba synthesized in the previous step, 50mL of absolute ethyl alcohol and 2.0g of potassium carbonate, putting the obtained mixture into a 250mL three-neck flask, plugging the bottle mouths on two sides with turning plugs, opening an electric stirrer, and adding 4.5g of bromoundecane under stirring;
placing the three-neck flask in an oil bath kettle, setting the temperature to 65 ℃ and refluxing the reactants for 12 hours; after 12h, the hot reaction solution was poured into 1000mL of ice water and stirred, which was followed by removal of the potassium carbonate; filtering, washing the obtained solid with a large amount of petroleum ether, and removing unreacted bromoundecane; performing secondary suction filtration, and drying the obtained solid in a drying oven; to obtain a product of higher purity, purification is carried out by column chromatography, first using petroleum ether: dichloromethane ═ 2: 1 (volume ratio) as a solvent, the first component in the sample was removed, and then petroleum ether: dichloromethane elution ═ 1: 2 (volume ratio), collecting the second component; the collected second fractions were dried to yield 8.7g of a light yellow solid in about 94% yield, which gave the product as Azo 11.
1.3) preparation of multiple-response shape memory polyurethane composite A-SMPU10
(1) Weighing 2.5g of SMPU10, placing the SMPU10 in a glass bottle, adding a DMF solvent into the glass bottle, placing the glass bottle in an oil bath kettle at the temperature of 80 ℃, and stirring;
(2) after the SMPU10 is completely dissolved, 2.218g of Azo11 is added into the mixture for reaction for 2 hours;
(3) after the reaction is finished, pouring the reaction solution into a preheated mold, and placing the mold in an oven at 80 ℃ for drying for 8 hours to obtain the multiple response shape memory polyurethane composite material named A-SMPU 10.
The synthetic route of SMPU10 in the invention is as follows:
the synthetic route of the Azo11 of the invention is as follows:
secondly, the performance test of the star-shaped multi-response shape memory polyurethane composite material prepared by the invention
1、1H NMR analysis
The structure of the sample can be analyzed by analyzing nuclear magnetic resonance spectroscopy. The specific operation steps are as follows: clamping a small amount of SMPU10 cut by a forceps, placing the SMPU10 into two nuclear magnetic tubes, respectively pouring Deuterated Chloroform (DCAS), covering the nuclear magnetic tubes, shaking uniformly to dissolve SMPU10 to obtain a sample to be tested, highly calibrating the sample, extending a probe into the sample, entering a test page to select experimental types and parameters, then carrying out field locking and automatic shimming, and processing and exporting data after completion. By performing nmr analysis on the sample, the composition and structure of the sample can be known.
As can be seen from fig. 1, the hydrogen energy on the SMPU10 structure finds the corresponding peak in the map, and the peak area ratio corresponds to the number ratio of protons at different positions of SMPU 10. In addition, other miscellaneous peaks except for the solvents CDCl3 and TMS are not seen in the map, which indicates that the SMPU10 with higher purity is successfully synthesized.
2. Infrared test (FT-IR)
The structure of the sample can be further analyzed on the basis of nuclear magnetism through infrared spectrum testing. The method comprises the following steps: cutting the sample into small square tablets of about 1cm multiplied by 1cm to prepare a sample to be detected; and after the potassium bromide blank sheet collects the reference background spectrum, putting the sample to be detected on a sample frame, measuring and processing the spectrum, and then exporting the spectrum. By analyzing the infrared spectrum data, the composition of molecular chain groups in the sample can be known so as to determine whether the target product is synthesized. And determining whether a target product is synthesized.
FIG. 2 shows the infrared spectra of SMPU10 and A-SMPU10 obtained by our test. From the infrared spectrum curve of SMPU10 in fig. 2, it can be seen that C ═ O in carbamate appears at 1724cm "1, an absorption peak of N — H in carbamate appears at 3336 cm" 1, and no absorption peak of isocyanate appears at 2270cm "1, indicating that no isocyanate exists in the product, the isocyanate in the raw material completely participates in the reaction, and the final product obtained by the experiment is polyurethane SMPU 10.
As can be seen from the A-SMPU10 IR spectrum of FIG. 2, absorption peaks appeared at both 1724cm-1 and 3332cm-1, indicating that after the addition of Azo11, the carbamate groups in the original SMPU10 were not destroyed; two new peaks appear at 1470cm-1 and 1727cm-1, wherein 1470cm-1 is a characteristic peak of an N-N bond, which indicates that the N-N group in the Azo11 is not destroyed and successfully introduced when the Azo11 is added into the composite material for blending, and the N-N group is introduced, so that the A-SMPU10 can be subjected to bending deformation under the irradiation condition of a certain wavelength and has photoresponse performance; 1724cm-1 this peak is the characteristic peak of C ═ O on the benzene ring due to stretching vibration, indicating that Azo11 was successfully attached to SMPU 10; the absorption peak at 3000-3100 cm < -1 > is a C-H stretching vibration peak on a benzene ring; there is a C-H absorption peak at 1546cm-1 on the benzene ring, indicating that no substitution reaction occurs with the hydrogen atom on the benzene ring of Azo11 during blending.
2. X-ray diffraction analysis (XRD)
The sample is made into a small square about 1cm multiplied by 1cm for testing. The crystallization condition of the internal molecules in the sample and the crystal structure of the molecules can be known by analyzing the X-ray diffraction pattern of the sample.
FIG. 3 is an X-ray diffraction diagram of SMPU10 and A-SMPU 10. As shown in the figure, in all samples, a plurality of sharp and strong diffraction peaks appear in a wide-angle region of 2 θ -5 ° to 35 °, which indicates that the samples are all crystalline substances and have good crystallinity; the sharp diffraction peak of SMPU10 appears in the wide-angle region, 2 θ is 21.3 ° and 23.6 °, which are the (110) and (200) crystal planes of PCL; in the X-ray diffraction curve of a-SMPU10, sharp diffraction peaks appeared in the vicinity of both 2 θ ═ 21 ° and 23 °, which are crystalline peaks of PCL soft segment, indicating that the product after blending was still a crystalline material; comparing the peaks of the two curves at three positions of 2 theta, 21 degrees, 23 degrees and 29 degrees, the a-SMPU10 is sharper than SMPU10, which shows that the addition of the blending substance promotes the crystallization of the PCL soft segment, and the diffraction peak of the blending substance also appears in the high-angle region, so that the addition substance crystallization and the PCL crystallization coexist, and the shape fixation of the polymer is enhanced.
3. Analysis of thermal Properties
3.1) TG analysis
Starting the instrument for 30min, standing for the instrument to be stable, placing a sample on a testing rod of the instrument by using a ceramic crucible, and heating the sample to 600 ℃ from 40 ℃ at a speed of 20 ℃/min under the nitrogen purging to finish the test. The TG test allows to know the thermal stability and the thermal decomposition temperature of the sample.
FIG. 4 is a thermogravimetric plot of SMPU10 and A-SMPU 10. As can be seen from the thermal weight loss curve of the SMPU10, the thermal weight loss curve has two decomposition platforms, wherein the first decomposition platform is the decomposition of a PCL soft segment, the decomposition temperature is 230-290 ℃, the second decomposition platform is the decomposition of a PCL hard segment, the decomposition temperature is 290-470 ℃, and the SMPU10 is a microphase separation structure and consists of the soft segment and the soft segment; A-SMPU10 is similar to SMPU10, and two decomposition platforms appear, which shows that the addition of the Azo11 and the cyanobiphenylene does not destroy the original structure of the PCL; as can be seen from the figure, the decomposition temperature of A-SMPU10 is slightly increased compared with that of SMPU10, and the reduction speed is not greatly different, and the analysis is probably because the number of hydrogen bond structures between soft segments and soft segments is increased after SMPU10 is added into the Azo11, and the hydrogen bonds promote the crystallization of the soft segments, so that the decomposition temperature of the soft segments and the soft segments of the compound is slightly increased. Through the above analysis, it is shown that both SMPU10 and A-SMPU10 have two decomposition platforms, and have microphase separation structures, so that the material has shape memory property.
3.2) DSC analysis
Weighing about 5mg of sample by using an analytical balance, flattening the sample in an aluminum dish, pricking a small hole on a cover, and covering and punching the small hole to obtain a sample; and (3) filling nitrogen to test in a nitrogen atmosphere, raising the temperature from minus 20 ℃ to 200 ℃ at a speed of 10 ℃/min, and then lowering the temperature from 20 ℃ to minus 20 ℃ at a cooling speed of 10 ℃/min to finish the test. By analyzing the DSC chart of the test, the glass transition temperature of the sample can be known.
FIG. 5 is a DSC of SMPU10 and A-SMPU 10. As can be seen from the first cooling curve of fig. 5(a), a-SMPU10 has two more gradual cold crystallization peaks in the soft segment compared to SMPU10, indicating that the ability of SMPU10 to crystallize is enhanced by the addition of Azo11, probably because the addition of Azo11 monomer promotes microphase separation of SMPU10 to further crystallize the soft segment of SMPU 10; also, no crystallization peak was observed for the long chain alkoxy tails of Azo11 after addition of Azo11 monomer, probably because the presence of the polyurethane phase prevented crystallization of the Azo11 alkoxy tails.
As can be seen from the second temperature rise curve of fig. 5(b), compared with SMPU10, soft-segment crystal melting occurs at the 25 ℃ position in a-SMPU10, probably due to the stable stacked ordered structure formed between some Azo11 molecules, which promotes the crystallization of SMPU 10; the glass transition temperature of a-SMPU10 was reduced compared to SMPU10, probably because the incorporation of Azo11 impaired the ability of the hard segments to bond to each other in SMPU 10.
From the above analysis, it is demonstrated that both SMPU10 and A-SMPU10 have multiple phases coexisting, and it is because the multiple phases coexisting, the material has shape memory property with multiple responses.
4. Characterization of macroscopic shape memory Properties
4.1) macroscopic shape memory Properties of thermotropic SMPU
a) SMPU10 material
In order to more intuitively study the thermal responsiveness, the experiment used a drying oven as a heat source to test the heat recovery shape memory performance of SMPU 10. Cutting a square spline of 3.5 × 3.5cm from SMPU10 film at room temperature, and coating the middle with a shape as a contrast, as shown in FIG. 6a, to obtain the original shape; placing the sample strip in a drying oven with the set temperature of 80 ℃ for starting heating, and when the temperature of the drying oven gradually rises, softening the sample strip; continuing to heat to 80 ℃, keeping the temperature for 5min, folding four corners inwards in the drying oven, namely the shape of the film, keeping the folded shape, taking out the film, placing the film on an ice bag, and rapidly cooling to fix the shape, namely obtaining the fixed temporary shape shown in figure 6 b; in order to observe the thermal response property, the sample bar fixed with the temporary shape was placed in a drying oven set at 30 ℃, and it was observed that the sample bar was gradually softened and the four folded corners were opened outward as shown in fig. 6 c; the temperature was raised to 50 ℃ as shown in fig. 6d, the bars were opened more; the temperature is raised to 70 ℃, as shown in fig. 6e, the folded place is basically unfolded and tends to be flat; by raising the temperature to 80 ℃ and holding it for 1min, the shape of the bars was observed to revert to FIG. 6f, consistent with the original shape (FIG. 6 a).
b)A-SMPU10
The thermally responsive shape memory recovery procedure of A-SMPU10 was obtained as in the thermally responsive shape memory recovery experimental procedure of SMPU10 above. FIG. 7a is the initial shape of A-SMPU 10; FIG. 7b is a temporary shape after the four corners are folded after the temperature is raised to 40 ℃ and the temperature is kept for 5min, and then the folded product is placed on an ice bag to be rapidly cooled and fixed; the temporary shape-fixed sample bars were then returned to the oven, set at 25 ℃, and the sample bars were observed to gradually soften, with the four folded corners splaying outward as shown in fig. 7 c; the temperature was raised to 30 ℃ as shown in fig. 7d, the bars were opened more; the temperature is raised to 35 ℃, as in fig. 7e, the folded place is substantially unfolded and tends to be flat; by raising the temperature to 40 ℃ and holding it for 1min, the shape of the bars was observed to revert to FIG. 7f, consistent with the original shape (FIG. 7 a).
4.2) macroscopic shape memory Properties of photothermal Dual response
a)A-SMPU10
In order to test the light response performance of the A-SMPU10, an ultraviolet device is used for testing in the experiment, and then a drying oven is used for researching the heat response performance of the A-SMPU 10. The sample was pre-conditioned by cutting a rectangular strip of the A-SMPU10 film at room temperature, as shown in FIG. 8a, which is the original shape of the strip; placing the sample strip in a drying oven with a set temperature of 40 ℃ for heating, keeping the temperature constant for 5min, softening the sample strip when the temperature of the drying oven gradually rises, stretching the sample strip in the drying oven, taking out the sample strip, and rapidly cooling the sample strip on an ice bag to fix the shape of the sample strip, namely obtaining a fixed temporary shape shown in figure 8 b; the stretched bars were pre-treated samples to facilitate the following photo-thermal testing.
Irradiating the pretreated sample strip with ultraviolet light, wherein the sample is slightly bent after the ultraviolet light is irradiated for 5s, as shown in figure 9 a; after 2min of uv irradiation, the sample curls, as shown in fig. 9 b.
The bars with the temporary shape fixed are then placed back in the 40 ℃ drying oven and the shape of the bars (fig. 10a) is observed to gradually return to the original shape (fig. 10 b).
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (7)
1. A star-shaped multi-response shape memory polyurethane composite material is characterized in that the structural formula of the composite material is as follows:
wherein n, k and m all represent the polymerization degree and can be any positive integer;
is composed of
R is
2. The preparation method of the star-shaped multi-response shape memory polyurethane composite material of claim 1, which comprises the following steps:
(1) weighing 2.5-3.5g of SMPU10, placing in a glass bottle, adding DMF solvent, placing the glass bottle in an oil bath kettle at 80 ℃, and stirring;
(2) after the SMPU10 is completely dissolved, 1.0-2.5g of Azo11 is added into the mixture for reaction for 2 hours;
(3) and after the reaction is finished, pouring the reaction solution into a preheated mold, and placing the mold in an oven at 80 ℃ for drying for 8-10h to obtain the multi-response shape memory polyurethane composite material.
3. The preparation method of the star-shaped multi-response shape memory polyurethane composite material as claimed in claim 2, wherein the SMPU10 is synthesized by the following steps;
(1) prepolymerization reaction: weighing 5.00g of PCL, placing the PCL in a reactor, adding 18-25mL of DMF and 3-6 drops of hexamethylene diisocyanate, adding a catalyst, placing the reactor in an oil bath pot, stirring and heating to 80-90 ℃, wherein the stirring speed is 400-500 r/min, adding 0.8-0.9mL of hexamethylene diisocyanate into the reactor, and reacting for 1 h;
(2) chain extension reaction: at the reaction temperature, adding 2.6-3.0g of solid N, N dihydroxyethyl isonicotine into the reactor, adding 2.0-5.0mL of hexamethylene diisocyanate, and reacting for 2-4 h;
(3) and (3) crosslinking reaction: adding 0.3-0.5g of glycerol into the reaction liquid in the step (2), and reacting for 2 hours;
(4) film forming: and pouring the liquid after the reaction into a preheated mould, uniformly distributing the liquid on the mould, and placing the mould in an oven at 80 ℃ for drying for 8-20h to obtain the shape memory polyurethane SMPU 10.
4. The method for preparing the star-shaped multi-response shape memory polyurethane composite material according to claim 3, wherein the molecular weight of the PCL is 2000, and the PCL is dried in an oven at 80 ℃ before use.
5. The method of preparing a star-shaped multiple-response shape memory polyurethane composite of claim 3, wherein the catalyst is dibutyltin dilaurate.
6. The preparation method of the star-shaped multi-response shape memory polyurethane composite material as claimed in claim 2, wherein the synthetic method of the Azo11 is as follows:
(1) putting 5.0g of Azoba, 50mL of absolute ethyl alcohol and 2.0g of potassium carbonate into a reactor, adding 4.3-4.5g of bromoundecane into the reactor while stirring, and putting the reactor into a 65 ℃ oil bath to react for 12 hours;
(2) after the reaction is finished, the reaction solution is poured into 1000mL of ice water while the reaction solution is hot, stirred, filtered, washed and dried to obtain solid Azo 11.
7. The preparation method of the star-shaped multiple-response shape memory polyurethane composite material as claimed in claim 6, wherein the synthetic method of the azo ba is as follows:
(1) preparing a sodium hydroxide solution and a glucose solution;
(2) weighing 10.0-15.0g of p-nitrobenzoic acid monomer into a reactor, adding the sodium hydroxide solution into the reactor for dissolution, placing the reactor into an oil bath kettle at 50-60 ℃, heating for 10-20min, adding the glucose solution into the reactor, and reacting at 50-60 ℃ for 8-10 h;
(3) and after the reaction is finished, pouring out the reaction liquid, cooling to room temperature, adding a dilute acetic acid solution with the mass fraction of 15% into the reaction liquid, adjusting the pH value to 6, performing suction filtration and washing, then adding the solution into a hot potassium carbonate solution, performing suction filtration again after the potassium carbonate solution is cooled and a solid is separated out, washing the obtained solid to be neutral by water, and drying to obtain a light yellow powdery solid, namely the Azoba.
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